Assessing and forecasting the impacts of global change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins

Introduction

The Consolider-Ingenio 2010 project SCARCE, with the full title ??Assessing and predicting effects on water quantity and quality in Iberian Rivers caused by global change?? aims to examine and predict the relevance of global change on water availability, water quality, and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well as their socio-economic impacts. Starting in December 2009, it brought together a multidisciplinary team of 11 partner Spanish institutions, as well as the active involvement of water authorities, river basin managers, and other relevant agents as stakeholders.

Methods

The study areas are the Llobregat, Ebro, Jucar, and Guadalquivir river basins. These basins have been included in previous studies and projects, the majority of whom considered some of the aspects included in SCARCE but individually. Historical data will be used as a starting point of the project but also to obtain longer time series. The main added value of SCARCE project is the inclusion of scientific disciplines ranging from hydrology, geomorphology, ecology, chemistry, and ecotoxicology, to engineering, modeling, and economy, in an unprecedented effort in the Mediterranean area. The project performs data mining, field, and lab research as well as modeling and upscaling of the findings to apply them to the entire river basin.

Results

Scales ranging from the laboratory to river basins are addressed with the potential to help improve river basin management. The project emphasizes, thus, linking basic research and management practices in a single framework. In fact, one of the main objectives of SCARCE is to act as a bridge between the scientific and the management and to transform research results on management keys and tools for improving the River Basin Management Plans. Here, we outline the general structure of the project and the activities conducted within the ten Work Packages of SCARCE.     

Levels and seasonal variations of organochlorine pesticides in urban and rural background air of southern Ghana

Urban, suburban and rural background air samples were collected in southern Ghana in 2008 employing polyurethane foam disc passive air samplers (PAS). PAS were analysed for organochlorine pesticides (OCPs), namely hexachlorocyclohexanes (α-, β-, γ- and δ-hexachlorocyclohexane), dichlorodiphenyltrichloroethane including metabolites (o,p'- and p,p'-DDT, DDE and DDD), hexachlorobenzene, pentachlorobenzene, aldrin, dieldrin, endrins (endrin, endrin aldehyde and endrin ketone), isodrin, heptachlors (heptachlor, heptachlor epoxide A and heptachlor epoxide B), chlordanes (α-, β-chlordane, oxychlordane and trans-nonachlor), endosulfans (α- and β-endosulfan and endosulfan sulphate), methoxychlor and mirex using a gas chromatograph coupled to a mass spectrometer. The levels of OCPs ranged for the individual pesticides from below limit of quantification to 750 pg m(-3) (for α-endosulfan), and current agricultural application seemed to be the main primary source of most abundant pesticides. Re-volatilization of previously used pesticides from contaminated soils could not be ruled out either as potential secondary source of contamination, especially in warm and dry seasons and periods of intensive agricultural activities. Higher atmospheric concentrations were observed in November and December during the dry season compared to lower concentrations observed in June, July and August when the country experiences heavy rains. The highest seasonal variation was observed for currently used pesticides as α-endosulfan. A p,p'-DDT/p,p'-DDE ratio suggested recent inputs of fresh technical DDT.     

Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Fifteen years of monitoring of POPs in the breast milk, Czech Republic, 1994–2009: trends and factors

Background, aim and scope

The breast milk has been recommended to carry out as a monitoring tool for effectiveness evaluation of the Stockholm Convention on Persistent Organic Pollutants (POPs). Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloro-ethane (DDT) and its metabolites (DDX), hexachlorbenzene (HCB) and isomers of hexachlocyklohexane (HCHs) have been monitored in the breast milk of nursing mothers in the Czech Republic since 1994 as a part of The Environmental Health Monitoring System. Knowledge about long-term POPs distribution and accumulation in the human body is crucial to understanding uptake, degradation and subsequent effects as well as to conduct risk assessments. The main aim of this study is to evaluate 15-years long-term trends of selected POPs in human milk in the Czech Republic and to elucidate the questionnaire information about the age, parity and social habits, to the final concentrations. This effectiveness evaluation of POPs restriction is quite precisely after 15-years monitoring campaigns.

Materials, methods and results

The human milk samples (4,753 samples) were analysed for a number of chlorinated organic chemicals including PCBs and selected chlorinated pesticides (OCPs, HCB, HCHs, DDX). The relative change of concentration per year for all chemicals was analysed. The remaining percentages of POPs in breast milk in comparison to 1994 are also expressed. Czech population half-lives of POPs in breast milk, derived from either linear or exponential models were computed.

Conclusions and perspectives

The long-term data indicates a continuation of a decreasing trend of POPs concentrations on breast milk. Our study did not confirm lactation and parity as an important outflux resulting in the decrease in concentrations in mothers, which is in the antagonism with most of the studies. The higher BMI was associated with higher amounts of HCB and lower amounts of higher chlorinated PCBs. The results confirm the effectiveness of restrictions of POPs usage in the Czech Republic. This ongoing long-term study is very useful tool for parametric effectiveness evaluation of Stockholm Convention.     

Influences of natural emission sources (wildfires and Saharan dust) on the urban organic aerosol in Barcelona (Western Mediterranean Basis) during a PM event

The urban air quality in Barcelona in the Western Mediterranean Basin is characterized by overall high particulate matter (PM) concentrations, due to intensive local anthropogenic emissions and specific meteorological conditions. Moreover, on several days, especially in summer, natural PM sources, such as long-range transported Saharan dust from Northern Africa or wildfires on the Iberian Peninsula and around the Mediterranean Basin, may influence the levels and composition of the organic aerosol. In the second half of July 2009, daily collected PM₁₀ filter samples in an urban background site in Barcelona were analyzed on organic tracer compounds representing several emission sources. During this period, an important PM peak event was observed. Individual organic compound concentrations increased two to five times during this event. Although highest increase was observed for the organic tracer of biomass burning, the contribution to the organic aerosol was estimated to be around 6?%. Organic tracers that could be related to Saharan dust showed no correlation with the PM and OC levels, while this was the case for those related to fossil fuel combustion from traffic emissions. Moreover, a change in the meteorological conditions gave way to an overall increase of the urban background contamination. Long-range atmospheric transport of organic compounds from primary emissions sources (i.e., wildfires and Saharan dust) has a relatively moderate impact on the organic aerosol in an urban area where the local emissions are dominating.     

Investigating phosphorus limitation in a fixed bed filter with phosphorus and nitrogen profile measurements

In 2000, the European Union adopted the European Water Framework Directive (WFD) (European Commission, 2000). The WFD focuses on increasingly stringent nutrient standards including ultra low nitrogen (< 2.2 mg N-total/L) and phosphorus concentrations (< 0.15 mg total phosphorus/L) in receiving surface waters and in relevant point sources like wastewater treatment plant (WWTP) effluent. Expansion of WWTPs with advanced post-treatment processes, like effluent filtration, is widely proposed to meet possible future effluent discharge standards. When combining biological nitrate-nitrogen and chemical phosphorus removal in one filter, phosphorus limitation in the denitrifying process may occur. This study investigated where in the filter bed and under which conditions phosphorus limitation occurs. Profile measurements for nitrate, nitrite, and orthophosphorus (PO4-P) combined with chemical oxygen demand (COD) and 02 were conducted. Results showed that the required PO4-P/NOx-N ratio is approximately 0.006 mg/mg after phosphorous precipitation and flocculation. Profile measurements have proven to be an applicable and useful tool. It showed how nitrate and orthophosphorus are removed through the filter bed based on the PO4-P/NOx-N ratio. When orthophosphorus is removed more rapidly and efficiently compared to nitrate, the PO4-P/NOx-N ratio decreases. When PO4-P/NOx-N ratio thresholds are approximately 0.006 mg/mg for a certain period of time and water temperatures varied significantly, orthophosphorus limitation may occur. Changing the filter-bed configuration or decreasing the coagulant dosage can prevent limitation of the denitrifying process because of a phosphorous shortage.     

Particulate matter emission rates from beef cattle feedlots in Kansas-reverse dispersion modeling

Open beef cattle feedlots emit various air pollutants, including particulate matter (PM) with equivalent aerodynamic diameter of 10 microm or less (PM10); however limited research has quantified PM10 emission rates from feedlots. This research was conducted to determine emission rates of PM10 from large cattle feedlots in Kansas. Concentrations of PM10 at the downwind and upwind edges of two large cattle feedlots (KS1 and KS2) in Kansas were measured with tapered element oscillating microbalance (TEOM) PM10 monitors from January 2007 to December 2008. Weather conditions at the feedlots were also monitored. From measured PM10 concentrations and weather conditions, PM10 emission rates were determined using reverse modeling with the American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model (AERMOD). The two feedlots differed significantly in median PM10 emission flux (1.60 g/m2-day for KS1 vs. 1.10 g/m2-day for KS2) but not in PM10 emission factor (27 kg/1000 head-day for KS1 and 30 kg/1000 head-day KS2). These emission factors were smaller than published U.S. Environmental Protection Agency (EPA) emission factor for cattle feedlots.     

Evaluating the degradation of the herbicides picloram and 2,4-D in a compartmentalized reactive biobarrier with internal liquid recirculation

Tordon is a widely used herbicide formulation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-amino-3,5,6-trichloropicolinic acid (picloram), and it is considered a toxic herbicide. The purposes of this work were to assess the feasibility of a microbial consortium inoculated in a lab-scale compartmentalized biobarrier, to remove these herbicides, and isolate, identify, and evaluate their predominant microbial constituents. Volumetric loading rates of herbicides ranging from 31.2 to 143.9 g m^?3 day^?1, for 2,4-D, and 12.8 to 59.3 g m^?3 day^?1 for picloram were probed; however, the top operational limit of the biobarrier, detected by a decay in the removal efficiency, was not reached. At the highest loading rates probed, high average removal efficiencies of 2,4-D, 99.56?±?0.44; picloram, 94.58?±?2.62; and chemical oxygen demand (COD), 89.42?±?3.68, were obtained. It was found that the lab-scale biofilm reactor efficiently removed both herbicides at dilution rates ranging from 0.92 to 4.23 day^?1, corresponding to hydraulic retention times from 1.087 to 0.236 days. On the other hand, few microbial strains able to degrade picloram are reported in the literature. In this work, three of the nine bacterial strains isolated cometabolically degrade picloram. They were identified as Hydrocarboniphaga sp., Tsukamurella sp., and Cupriavidus sp.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.